Sulfonated amino-phthalalkylolimides



Patented Nov. 4, 1947 1 SULFONATED AMINO-PHTHALALKYLOL IIVIIDES HaroldT. L acey', Plainfield, and Robert E. Broulls lard, Somerville, N. J.,assignors to American poration of Maine Cyanamid Company, New York, N.Y., a cor- No Drawing. Application January 12, 194 Serial No. 572,580 76 Claims; (01. 854) This invention relates to a series of fluorescentcompounds, to a method of producing them, and to nitrogenous fiberscolored therewith.

Fluorescent fibers have become an interesting product of the textileindustry. They are used in producing colorless textiles and prints whichare visible under ultra-violet light and which have been adapted to'wideuse in advertising, decoration, exhibitions and in stage work. Manynovel, beautiful and variable efiects can be obtained by their use. Forexample, in entertainment centers this phenomenon has been effectivelyused to change the appearance of even the entire room simply by changingthe wave length of the light used for illumination to the ultra-violetend of the spectrum. Such materials also have been variously used inrugs, upholstery and furnishings in theatres or other buildings whichare kept in semi-darkness. The usual blind sensation encountered onentering such an auditorium is overcome by the glow emitted from thetreated materials under theinfluence of ultra-violet radiations.

According to this invention, the desired efiect on nitrogenous fibers,such as wool, silk, aralac and the like, i obtained by dyeing thesefibers directly with a sulfonated aminophthalalkylolimide capable ofrepresentation by the following structural formula:

in which R is a member of the group comprising hydrogen and substitutedor unsubstituted hydrocarbon radicals and R is an alkylol radical. Thepreparation of the aminophthalimides and aminophthalalkylolimides isfully set forth in our copending applications, Serial Nos. 547,988 (nowU. S. Patent 2,412,817) and 547,987, filed August 3, 1944, of the formerof which the present application is a continuation-in-part.

It will be noted from the above general formula that R may be ahydrocarbon radical. The range of equivalents from which it may beselected is very wide. For example, it may be an alkyl radical, such asmethyl, ethyl, propyl, butyl, and the like. The alkyl radicals may besubstituted, as for example in such hydroxyalkyl groups as methylol,ethylol and the like, or in halogenated alkyl radicals such aschloroethyl and the like, or may be an alkenyl radical such as allyl,methallyl and the like. R also may be a substituted and unsubstitutedaryl radical, such as phenyl, chlorophenyl, naphthyl, aminonaphthyl, andthe like; an aralkyl radical, such as benzyl, chlorobenzyl,naphthomethyl, nitronaphthomethyl and the like; or a saturated cyclicradical, such as cyclohexyl, methylcyclohexyl and the like. R may besubstantially any of the lower alkylol radicals containing from about1-4 carbon atoms. A typical example of compounds which are contemplatedin the scope of the present invention is sulfonated3-aminophthalethylolimide.

As noted in our above-mentioned copending applications, the substitutedphthalimides of the present invention may be prepared by any suitablemethod. One such procedure is to prepare a salt of suitable phthalimideand treat the latter with a halide of the radical which is to be at=tached to the imide nitrogen. At the same time,

or subsequently thereto, the other nitrogen oi the aminophthalimide maybe substituted. Or, if desired, a halophthalic acid or its anhydride maybe treated with an alkylolamine to form analkylolaminophthalalkylolamide which on heating is easily ring-closed tothe imide.

Perhaps the simplest method in operation, and the most economical tocarry out, is the preferred method in which a nitrophthalic acid iscondensed with an amine and the resultant amide is heated suflicientlyto be dehydrated to the nitroimide. The nitro group can then be reducedby any known method. The aminophthalimide so produced may then betreated if so desired to substitute in the amino group. Howeverprepared, the aminophthalimides are then sulfurated to produce thedyestuffs of this invention.

In general, the sulfonated aminophthalimides fiuoresce a bright blue invery dilute solutions but the shade gradually turns to a yellow-green asthe solutions become more concentrated. When nitrogenous ,fibers, suchas wool, are dyed with sulfonated aminophthalimides, dyeings areobtained which are white or very pale yellow in daylight and brilliantblue to yellow-green under ultra-violet light. When strong daylightshades are desired the sulfonated aminophthalimides may be incorporatedwith nonfluorescent dyestuffs to produce dyeings which under ordinarylight possess the color characteristics of the nonfiuorescent dye andwhich, under ultra-violet light, fiuoresce in the shade of. thenon-fluores cent dyestufi. Thus, when a mixture of Naph- 3 thalene AcidGreen V (C. I. 735) and sulfonated 3-aminophthalethylolimide is dyed onwool, a bright green dyeing is produced. The color properties arecomparable in either daylight or ultra-violet light.

The invention will be more fully illustrated in connection with thefollowing examples which are illustrative only and not by way oflimitation. All parts are by weight unlessotherwise noted.

Example 1 son! 53 parts of 3-nitrophthalic acid is slurried in 50 partsof water and 16.8 parts of monoethanolamine is added. An exothermicreaction results and the temperature of the reaction goes up to 60 C.The mixture is then heated to 160-165" C. until all evolution of waterhas ceased and for 30 min. longer. The mixture is then cooled to 70 C.and diluted with 100 parts of alcohol. After stirring to produce ahomogeneous mixture, the 3-nitrophthalethylolimide is added slowly to amixture of 94 parts of iron borings, 2 parts of -N-hydrochloric acid and125 parts of water. The addition requires about 30 min. The mixture isthen refluxed for one hour, after which the alcohol is removed bydistillation and water is added to maintain the original volume. Theiron slurry is filtered hot and the presscake washed with 25 parts ofwater at '95" C. The filtrate is cooled to l5-20 C. with stirring toprecipitate the 3-aminophthalethylolimide. The yellow crystallineproduct thus obtained melts at 145- 146 C. 25 parts of3-aminophthalethylolimide is added over a 5 min. period to 90 partsofsulfuric acid (D=1.84) at 95 CL The temperature of the sulfonatingmixture is maintained at 95- C. for 2 hours, after which it is drownedin a mixture of 150 parts of ice and 1-00 parts of water. After stirringfor 15 min. the precipitated, sulfonated aminophthalethylolimide isremoved by filtration, washed with a sodium sulfate solution and dried.The yellow, high-melting, sulfonated product thus obtained gives anaqueous solution which fluoresces blue-green.

parts of a wool skein is heated at substanfiially the boiling point in abath consisting of 3.2 part of sulfonated 3-aminophthalethylolimide, 1part of Glaubers salt, 0.4 part of 28% acetic acid and 350 parts ofwater for one-half hour, after which 0.3 part of sulfuric acid is addedand the boiling continued for an additional onehalf hour. The dyeing isthen rinsed and dried. The fibers thus produced have only a slightyellow cast in daylight and a brilliant yellow-green shade underultra-violet light.

Example 2 Example 3 was repeated substituting a primary propanolaminefor the monoethanolamine. The

product, after sulfonation, gave a wool dyeing of similar properties.

Example 3 Example 3 was repeated substituting a primary butanolamine forthe monoethanolamine. The

product after sulfonation gave a wool dyeing of similar properties.

Example 4 10 parts of a wool skein ls heated at substantially theboiling point in a bath consisting of 0.2 part of sulfonated3-aminophthalethylollmide, 0.2 part of Naphthalene Acid Green V (C. I.735), 1 part of Glaubers salt, 0.4 part of 28% acetic acid and 350 partsof water for one-half hour,

after which 0.3 part of sulfuric acid is added and the boiling continuedfor an additional one-half hour. The dyeing is then rinsed and dried.The product has a similar green shade in either daylight or ultra-violetlight.

Example 5 NCHzCHnOH som C 53 parts of l-nitrophthalic acid is slurriedin 50 parts of water, and 16.8 parts of monoethanolamine is added. Anexothermic reaction results and the temperature of the mixture goes upto 60 C. The reaction mixture is then heated to 160-165 C. until allevolution of water has ceased and for 30 min. longer. The mixture isthen cooled to 70 C. and diluted with 100 parts of alcohol. Afterstirring to produce a homogeneous mixture, the 4-nitrophthalethylolimideis added slowly to a previously boiled and cooled mixture of 94 parts ofiron borings, 2 parts of 5-N-hydrochloric acid and 125 parts of water.

The addition requires about 30 minutes. The mixture is then refluxed forone hour after which the alcohol is removed by distillation and water isadded to maintain the original volume. The iron slurry is filtered hotand the presscake washed with 25 parts of water at C. The filtrate iscooled to l5-20 C. with stirring to precipitate4-aminophthalethylolimide. It is a yellow crystalline solid melting at168 C.

25 parts of 4-aminophthalethylolimide is added over a 5 minute period to90, parts of sulfuric acid (D=1.84) at 95 C. The temperature of themixture is maintained at 95 C. for 2 hours after which it is drowned in150 parts of ice and parts of water. After stirring for 15 min. theprecipitated sulfonated 4-aminophthalethylolimide is removed byfiltration, washed with sodium sulfate solution, and dried. The yellow,high-melting, sulfonated product thus obtained gives aqueous solutionswhich fluoresce bluegreen.

10 parts of a wool skein is heated at substantially the boiling point ina bath consisting of 0.2 part of sulfonated 4-aminophthalethylolimide, 1part of Glaubers salt, 0.4 part of 28% acetic acid and 350 parts ofwater for one-half hour, after which 0.3 part of sulfuric acid is addedand the boiling continued for an additional onehalf hour. The dyeing isthen rinsed and dried. The fibers thus produced have only a slightyellow cast in daylight and a brilliant yellow-green shade underultra-violet light.

We claim:

1. As a dyestuif for nitrogenous fibers, a sulfonatedaminophthalalkylolimide.

2. As a dyestuff for nitrogenous fibers, a sulfonated3-aminophthalethylolimide.

3. As a dyestuif for nitrogenous fibers, a sulfonated4-aminophthalethyiolimide.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,446,860 Seyer Feb. 27, 19231,836,529 Eckert et a1 Dec. 15, 1931 2,273,444 Koeberle et a1 Feb. 17,1942 2,343,198 Moore Feb. 29, 1944 OTHER REFERENCES Mullins, AcetateSilk and its Dyes, (1927),

page 110.

Beilstein, 4th edition, vol. 22, page 534.

